Polyether nitrile and polyether nitrile particle

Abstract

A polyether nitrile represented by formula (I), wherein the "integrated value of peak A (peak having a peak top at 7.10-7.20 ppm) / integrated value of peak B (peak having a peak top at 7.55-7.68 ppm)" in a proton NMR measurement measured using a mixed solvent of pentafluorophenol and deuterated chloroform in a volume ratio of 5:4 is 0.050 or less. Provided is a polyether nitrile having high thermal stability.

Description

Polyethernitrile and polyethernitrile particles

[0001] The present invention relates to polyethernitriles and polyethernitrile particles.

[0002] Polyether nitrile is a type of super engineering plastic with advanced properties, including excellent thermal stability, chemical resistance, and flame retardancy, as well as excellent mechanical properties such as wear resistance and friction resistance.

[0003] Polyethernitrile has the above-mentioned high-level properties, but in recent years, the requirements for more advanced properties of materials have led to a demand for higher thermal stability.

[0004] In general, active functional group terminals present in a polymer are assumed to function as reaction sites for polymer reactions or as sites of interaction with additives, but also cause a decrease in thermal stability.Patent Document 1 discloses a method of using a mono-substituted halogen compound for the purpose of controlling the molecular weight during polymerization of polyether nitrile.

[0005] Japanese Unexamined Patent Publication No. 63-270733

[0006] However, the polyether nitrile described in Patent Document 1 did not sufficiently improve thermal stability. Furthermore, Patent Document 1 does not describe the mechanism or factors that enable control of the terminal structure and thermal stability. Furthermore, the method described in Patent Document 1 requires the use of a third component other than the monomer to block the polymer terminals, leaving room for improvement in processability and economic efficiency.

[0007] In view of the above problems of the prior art, the present inventors have an object to provide a polyether nitrile having excellent thermal stability.

[0008] The inventors of the present invention conducted extensive research to solve the above-mentioned problems and discovered an analytical method that enables the analysis and quantification of the terminal structure of polyethernitriles, which had been difficult to do in the past. Based on this analytical method, the inventors analyzed the relationship between the terminal structure of polyethernitriles and thermal stability, and discovered a method for controlling the terminal structure. The inventors then discovered that polyethernitriles that satisfy certain conditions have excellent thermal stability, thereby completing the present invention. Specifically, the present invention has the following features: (1) A polyethernitrile represented by formula (I), in which the "integral value of Peak A / integral value of Peak B" is 0.050 or less in proton NMR measurement using a mixed solvent of pentafluorophenol and deuterated chloroform in a volume ratio of 5:4:1: Peak A: A peak having a peak top at 7.10 to 7.20 ppm. Peak B: A peak having a peak top at 7.55 to 7.68 ppm.

[0009]

[0010] In formula (I), Ar is a unit represented by any one of formulas (a) to (f), and Ar may be composed of one type of unit or two or more types of units.

[0011]

[0012] (2) The polyethernitrile according to (1), wherein the "integral value of the peak showing the terminal / integral value of peak B" in proton NMR measurement using a mixed solvent of pentafluorophenol and deuterated chloroform in a volume ratio of 5:4 is 0.001 to 0.055. (3) The polyethernitrile according to (1) or (2), wherein Ar is composed of two or more types of units. (4) Polyethernitrile particles made of the polyethernitrile according to any one of (1) to (3), wherein the number average particle diameter is 0.1 to 200 μm. (5) A mobility member comprising the polyethernitrile according to any one of (1) to (3). (6) A structural member comprising the polyethernitrile according to any one of (1) to (3). (7) A member for electric / electronic materials comprising the polyethernitrile according to any one of (1) to (3). (8) Mobility using the mobility member according to (5). (9) A structural material using the structural member according to (6). (10) An electric or electronic product using the electric or electronic material member according to (7).

[0013] According to the present invention, a polyether nitrile having excellent thermal stability can be provided.

[0014] The present invention will be described in detail below with reference to embodiments.

[0015] (1) Polyethernitrile The polyethernitrile of the present invention is a polyethernitrile represented by formula (I).

[0016]

[0017] In formula (I), Ar is a unit represented by any one of formulas (a) to (f). Ar may be composed of one type of unit or two or more types of units.

[0018]

[0019] In the polyethernitrile of the present invention, Ar may be composed of two or more types of units.

[0020] When Ar is composed of two types of units, and the number of repeating units represented by the first type of Ar contained in the polyethernitrile is N, and the number of repeating units represented by the second type of Ar is M, the content (molar ratio) of the repeating units represented by the first type of Ar relative to the total number of Ar is expressed as [N / (N+M)]. Note that the relationship between N and M here is N≧M. In this case, if a polyethernitrile with a lower melting point is desired, it is preferable that [N / (N+M)]<1.00. Furthermore, in order to obtain a polyethernitrile with high crystallinity, it is preferable that [N / (N+M)]<0.8. In order to obtain a polyethernitrile with excellent processability, a low melting point is preferable. On the other hand, in order to obtain a polyethernitrile with excellent mechanical properties, high crystallinity is preferable.

[0021] In addition, the polyether nitrile in the present invention may be terminally modified with an end-capping agent.

[0022] When the polyethernitrile of the present invention is measured by proton NMR using a mixed solvent of pentafluorophenol and deuterated chloroform in a volume ratio of 5:4, the ratio of the integral of Peak A to the integral of Peak B shown below, "integral of Peak A / integral of Peak B," is 0.050 or less. Peak A: A peak having a peak top at 7.10 to 7.20 ppm Peak B: A peak having a peak top at 7.55 to 7.68 ppm "integral of Peak A / integral of Peak B" is preferably 0.040 or less, more preferably 0.020 or less, and most preferably 0. Note that "integral of Peak A / integral of Peak B" is 0 or more.

[0023] Here, Peak A is a peak having a peak top at 7.10 to 7.20 ppm in proton NMR measurement. When multiple peaks exist in the range of 7.10 to 7.20 ppm, the integral value of Peak A refers to the sum of the integral values ​​of the multiple peaks in the range of 7.10 to 7.20 ppm. Furthermore, Peak B is a peak having a peak top at 7.55 to 7.68 ppm in proton NMR measurement. When multiple peaks exist in the range of 7.55 to 7.68 ppm, the integral value of Peak B refers to the sum of the integral values ​​of the multiple peaks in the range of 7.55 to 7.68 ppm.

[0024] When a polymer or additive other than polyethernitrile is contained, it is preferable to perform proton NMR measurement after removing the polymer or additive other than polyethernitrile.

[0025] Among the peaks representing aromatic rings at the polymer terminals of polyethernitrile, the peak A represents a proton adjacent to an active group of an aromatic ring having an active group that adversely affects thermal stability. When the active group is a hydroxyl group derived from a diol monomer, two proton peaks appear in the region of Peak A for each hydroxyl group terminal. Here, the hydroxyl group terminal refers to the hydroxyl group when the aromatic ring at the polymer terminal has a hydroxyl group.

[0026] The peak B indicates the protons of the aromatic ring having a nitrile contained in the repeating unit constituting the polymer chain of the polyether nitrile. In the region of peak B, one peak corresponding to one proton appears for each aromatic ring having a nitrile.

[0027] That is, "the integral value of Peak A / the integral value of Peak B" indicates the proportion of active groups at the polymer terminals of the polyethernitrile polymer chain that adversely affect thermal stability. Examples of active groups that adversely affect thermal stability include polar functional groups such as hydroxyl groups.

[0028] There are no particular limitations on the method for making the "integral value of peak A / integral value of peak B" equal to or less than 0.050, but this can be achieved, for example, by either of the following two methods.

[0029] As a method 1, in a method for producing a polyethernitrile described below, in the relationship between the aromatic compound substituted with two hydroxyl groups as a monomer and the aromatic compound having a benzonitrile skeleton substituted with two halogeno groups, it is preferable that the proportion of the aromatic compound having a benzonitrile skeleton substituted with two halogeno groups is in excess over the aromatic compound substituted with two hydroxyl groups in terms of molar ratio. In this case, in the polyethernitrile obtained by completing the polymerization, the amount of hydroxyl terminal groups derived from the aromatic compound substituted with two hydroxyl groups can be reduced, and the "integral value of Peak A / integral value of Peak B" can be made 0.050 or less.

[0030] In order to make the "integral value of Peak A / integral value of Peak B" ratio 0.050 or less, it is preferable to complete the polymerization by allowing the polymerization reaction to proceed for a sufficient reaction time. In order to complete the polymerization, it is preferable to carry out the reaction for 6 hours or more after the target maximum reaction temperature is reached. In order to confirm the completion of the polymerization, the reaction solution during polymerization is sampled and subjected to proton NMR measurement using a mixed solvent of pentafluorophenol and deuterated chloroform in a volume ratio of 5:4. Completion of the polymerization can be confirmed when the "integral value of the peak showing the terminal / integral value of Peak B" in the measured proton NMR measurement no longer changes.

[0031] When NMP is used as the polymerization solvent, the reaction time at 200° C. is preferably 6 to 10 hours, more preferably 8 to 10 hours, in order to complete the polymerization when the polymerization reaction is carried out at 200° C. Completion of the polymerization can be expected by carrying out the reaction at 200° C. for 6 hours or more.

[0032] Alternatively, as a second method, the hydroxyl terminals can be blocked by terminal modification using an end-capping agent, thereby reducing the number of hydroxyl terminals and making the "integral value of Peak A / integral value of Peak B" 0.050 or less. Examples of end-capping agents include compounds that react with phenolic hydroxyl groups, such as organic halides. Adding an end-capping agent when polymerizing polyethernitrile or when blending polyethernitrile with other components can make the "integral value of Peak A / integral value of Peak B" 0.050 or less.

[0033] Method 1 is preferred in that it does not require a component other than the monomer, namely, an end-capping agent. Method 1 and Method 2 may also be used in combination.

[0034] The polyethernitrile of the present invention preferably has a "terminal peak integral / peak B integral" of 0.001 to 0.055 in proton NMR measurement using a mixed solvent of pentafluorophenol and deuterated chloroform in a volume ratio of 5:4. The "terminal peak integral / peak B integral" is an index representing the polymer length of the polyethernitrile. The larger the "terminal peak integral / peak B integral," the shorter the polymer length of the polyethernitrile. In order to obtain a polyethernitrile with high mechanical properties, a smaller "terminal peak integral / peak B integral" is preferred. In order to obtain a polyethernitrile with low viscosity and excellent processability, a larger "terminal peak integral / peak B integral" is preferred. Although the preferred range varies depending on the purpose, as a range in which the mechanical properties and processability of the polyether nitrile are compatible, the "integral value of the peak indicating the terminal / integral value of peak B" is more preferably 0.010 to 0.050, and even more preferably 0.020 to 0.040.

[0035] Regarding the peaks indicating the terminals, in the case of a polyethernitrile using only an aromatic compound substituted with two hydroxyl groups and an aromatic compound having a benzonitrile skeleton substituted with two halogeno groups as monomers, the terminal structure of the polymer will be a hydroxyl group terminal or a halogen terminal. As mentioned above, a hydroxyl group terminal is an aromatic ring having a hydroxyl group, and in proton NMR measurement, it is represented by Peak A, which has a peak top at 7.10 to 7.20 ppm. On the other hand, a halogen terminal is an aromatic ring having a halogen substituent. In proton NMR measurement, if the peak of the aromatic ring having a halogen substituent is designated as Peak C, Peak C has a peak top at 6.95 to 7.00 ppm. For each aromatic ring having a halogen substituent, a peak corresponding to one proton appears in the region of Peak C. Therefore, the aforementioned "integral value of the peak indicating the terminal" is the "sum of the integral values ​​of Peak A and Peak C" (hereinafter, sometimes referred to as the integral value of Peak (A + C)).

[0036] In the case of polyethernitriles in which terminal modifications are performed using an end-capping agent in addition to an aromatic compound substituted with two hydroxyl groups and an aromatic compound having a benzonitrile skeleton substituted with two halogeno groups as monomers, the "integral value of the peak indicating the terminal" is the "sum of the integral values ​​of Peak A, Peak C, and the peak derived from the end-capping agent." Peak A indicates the abundance of hydroxyl terminals, with a peak corresponding to two protons appearing per hydroxyl terminal. Peak C indicates a halogen terminal, with a peak corresponding to one halogen terminal appearing. When an end-capping agent is used to cap the hydroxyl terminals, the number of protons in the peak derived from the end-capping agent introduced at the terminal is converted to two protons and then summed, regardless of how many protons there are per structural unit (for example, one proton or four protons). That is, for example, when the number of protons of the peak derived from the end-capping agent in proton NMR measurement is 4 protons per structural unit, the integral value of the peak derived from the end-capping agent is divided by 2 to convert to an area value of 2 protons, and this is summed with the integral values ​​of Peak A and Peak C. Furthermore, when an end-capping agent that caps a halogen end is used, the number of protons of the peak derived from the end-capping agent introduced at the end is converted to 1 proton and summed, regardless of the number of protons per structural unit. That is, for example, when the number of protons of the peak derived from the end-capping agent in proton NMR measurement is 3 protons, the integral value of the peak derived from the end-capping agent is divided by 3 to convert to an area value of 1 proton, and this is summed with the integral values ​​of Peak A and Peak C.

[0037] The melting point of the polyether nitrile of the present invention is preferably 280 to 360°C, more preferably 280 to 350°C, from the viewpoint of processability.

[0038] The terminal group of the polyether nitrile of the present invention is not limited, but is usually a group selected from a hydroxyl group, a metal salt of a hydroxyl group, a halogeno group, a linear organic group having 1 to 16 carbon atoms, a branched organic group, and a cyclic organic group.

[0039] The polyethernitrile of the present invention has excellent thermal stability when measured by proton NMR using a mixed solvent of pentafluorophenol and deuterated chloroform in a volume ratio of 5:4, with a "peak A integral value / peak B integral value" ratio of 0.050 or less. In the present invention, "excellent thermal stability" means that, in thermogravimetric analysis (TG), the weight loss rate is small when heated in air from 50°C to melting point +30°C at a heating rate of 20°C / min and then held at melting point +30°C for 30 minutes, or, in rheometer measurement, the viscosity increase rate is small when heated in air at melting point +30°C for 30 minutes. More preferably, the polyethernitrile of the present invention has a small weight loss rate when heated in air from 50°C to melting point +30°C at a heating rate of 20°C / min and then held at melting point +30°C for 30 minutes in thermogravimetric analysis (TG), and a small viscosity increase rate when held in air at melting point +30°C for 30 minutes in rheometer measurement.

[0040] In thermogravimetric analysis (TG), the polyether nitrile of the present invention preferably exhibits a weight loss of 0.8% or less, more preferably 0.6% or less, and even more preferably 0.4% or less when heated in air from 50° C. to 30° C. above the melting point at a temperature increase rate of 20° C. / min and then held at 30° C. above the melting point for 30 minutes. The weight loss is calculated based on the weight after holding at 50° C. for 1 minute.

[0041] The polyether nitrile of the present invention preferably exhibits a viscosity increase rate of 70% or less, more preferably 60% or less, and even more preferably 35% or less, when maintained at 30°C above the melting point in air for 30 minutes in rheometer measurement. This viscosity increase is presumed to be due to oxidation in air. It is presumed that the presence of active terminals such as hydroxyl group terminals in the polyether nitrile accelerates the viscosity increase by oxidation in air.

[0042] The polyethernitrile of the present invention can be molded by, for example, injection molding, injection compression molding, blow molding, extrusion molding, etc. In molding, the polyethernitrile may be used alone, or, if desired, may be used as a composition containing inorganic fillers such as glass fiber, carbon fiber, titanium oxide, calcium carbonate, and additives such as antioxidants, heat stabilizers, ultraviolet absorbers, and colorants. In addition, resins other than the polyethernitrile of the present invention can also be blended in the molding.

[0043] The polyethernitrile of the present invention has excellent thermal stability and can be used for mobility components, electrical and electronic materials, structural materials, household and office electrical appliances, optical and precision machinery-related parts, plumbing components, and other industrial applications. Examples of mobility components of the present invention include components for automobiles, aircraft, ships, motorcycles, drones, urban air mobility, and kick scooters. Examples of electrical and electronic materials of the present invention include integrated circuits, connectors, and insulators. Examples of structural materials of the present invention include components for buildings, bridges, railways, roads, ports, and the like. The polyethernitrile of the present invention is particularly suitable for mobility components, electrical and electronic materials, and structural materials, which require excellent thermal stability.

[0044] Mobility devices using mobility components containing the polyethernitrile of the present invention exhibit excellent properties. Examples of the mobility devices of the present invention include automobiles, airplanes, ships, motorcycles, drones, urban air mobility, and kick scooters. Electrical and electronic products using electrical and electronic material components containing the polyethernitrile of the present invention exhibit excellent properties. Examples of the electrical and electronic products of the present invention include integrated circuits, connectors, and insulators.

[0045] Structural materials using structural members containing the polyethernitrile of the present invention exhibit excellent properties, and examples of the structural materials of the present invention include buildings, bridges, railways, roads, and ports.

[0046] The polyethernitrile particles of the present invention are polyethernitrile particles made from the polyethernitrile of the present invention and have a number average particle diameter of 0.1 to 200 μm or less. By setting the number average particle diameter to 200 μm or less, it is possible to easily achieve a uniform surface in coating films and the like made from the particles. Furthermore, by setting the number average particle diameter to 0.1 μm or more, it is possible to easily suppress aggregation of particles. It is preferable that the number average particle diameter of the polyethernitrile particles is 100 μm or less, as this allows them to be suitably used in applications such as powder coating. By setting the number average particle diameter to 100 μm or less, it is possible to achieve a uniform surface in coating films and the like made from the particles.

[0047] To obtain polyethernitrile particles having a number-average particle size within the above range, the particle formation conditions can be changed. For example, the number-average particle size can be controlled by changing the composition of the poor solvent, as described below. Other examples include pulverizing particles or polymer lumps, or dissolving and re-forming particles.

[0048] (2) Method for Producing Polyethernitrile The method for producing the polyethernitrile of the present invention is not particularly limited as long as it can synthesize a polyethernitrile that satisfies the requirement (1) above, and any production method can be adopted. For example, the polyethernitrile of the present invention can be produced by heating an aromatic compound substituted with two hydroxyl groups, an aromatic compound having a benzonitrile skeleton substituted with two halogeno groups, and a base in an organic polar solvent.

[0049] The aromatic compound substituted with two hydroxyl groups, the aromatic compound having a benzonitrile skeleton substituted with two halogeno groups, the base, the organic polar solvent, and the reaction conditions used in one example of the method for producing the polyethernitrile of the present invention will be described below.

[0050] Examples of the aromatic compound substituted with two hydroxyl groups, which is used as a monomer in the method for producing the polyethernitrile of the present invention, include compounds represented by any of the following general formulas (g) to (l):

[0051]

[0052] The aromatic compound substituted with two hydroxyl groups is preferably a compound selected from the group consisting of resorcinol, hydroquinone, 4,4'-dihydroxybiphenyl, 2,2'-bis(4-hydroxyphenyl)propane, and bis(4-hydroxyphenyl)sulfone. Two or more types of compounds substituted with two hydroxyl groups may be used.

[0053] The compound having a benzonitrile skeleton substituted with two halogeno groups, which is used as a monomer in the method for producing the polyether nitrile of the present invention, can be a compound represented by the following formula (m).

[0054]

[0055] X is a chlorine atom or a fluorine atom. Examples of the compound having a benzonitrile skeleton substituted with two halogeno groups include 2,6-dichlorobenzonitrile, 2,6-difluorobenzonitrile, and 2-chloro-6-fluorobenzonitrile, with 2,6-dichlorobenzonitrile being preferred.

[0056] The base used in the method for producing the polyethernitrile of the present invention includes organic bases and inorganic bases. Specific examples include organic bases such as 1,8-diazabicyclo[5.4.0]-7-undecene, 1,5-diazabicyclo[4.3.0]-5-nonene, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, and 1,5,7-triazabicyclo[4.4.0]dec-5-ene; alkali metal carbonates such as lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, and cesium carbonate; alkaline earth metal carbonates such as calcium carbonate, strontium carbonate, and barium carbonate; and carbonates of carbon dioxide particles. Examples of suitable bases include alkali metal bicarbonates such as lithium hydrogen carbonate, sodium bicarbonate, potassium bicarbonate, rubidium bicarbonate, and cesium bicarbonate; alkaline earth metal bicarbonates such as calcium bicarbonate, strontium bicarbonate, and barium bicarbonate; alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, and cesium hydroxide; and alkaline earth metal hydroxides such as calcium hydroxide, strontium hydroxide, and barium hydroxide. Among these, carbonates such as sodium carbonate and potassium carbonate and bicarbonates such as sodium bicarbonate and potassium bicarbonate are preferred from the standpoint of ease of handling and reactivity, with sodium carbonate being even more preferred. These bases may be used alone or in combination of two or more. These bases are preferably used in the form of anhydrides, but can also be used as hydrates or aqueous mixtures. The term "aqueous mixture" as used herein refers to an aqueous solution, a mixture of an aqueous solution and a solid component, or a mixture of water and a solid component.

[0057] The amount of base used in the method for producing the polyethernitrile of the present invention depends on the amount of the aromatic compound substituted with two hydroxyl groups. When a monovalent base is used, at least 2 equivalents are required relative to the aromatic compound substituted with two hydroxyl groups, preferably 2.2 equivalents or more, and more preferably 2.4 equivalents or more. By incorporating a sufficient amount of base, the "integral value of peak A / integral value of peak B" in proton NMR measurement of the resulting polyethernitrile measured using a mixed solvent of pentafluorophenol and deuterated chloroform in a volume ratio of 5:4 can be reduced. Furthermore, when a divalent base such as sodium carbonate is used, at least 1 equivalent is required relative to the aromatic compound substituted with two hydroxyl groups, preferably 1.1 equivalents or more, and more preferably 1.2 equivalents or more. Since the product can be produced even if an excess amount of base is used, there is no particular upper limit, but in reality it is 10 equivalents or less.

[0058] In the preferred method for producing the polyethernitrile of the present invention, the organic polar solvent used is not particularly limited as long as it does not inhibit the reaction. Specific examples of such organic polar solvents include nitrogen-containing polar solvents such as N-methyl-2-pyrrolidone (NMP), N-methylcaprolactam, N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), 1,3-dimethyl-2-imidazolidinone (DMI), hexamethylphosphoramide, and tetramethylurea; sulfoxide / sulfone solvents such as dimethyl sulfoxide (DMSO), dimethyl sulfone, diphenyl sulfone, and sulfolane; nitrile solvents such as benzonitrile; diaryl ethers such as diphenyl ether; ketones such as benzophenone and acetophenone; and mixtures thereof. These solvents are all preferably used due to their high reaction stability, and among them, solvents selected from NMP, DMSO, and sulfolane are preferred, with NMP being particularly preferred. These organic polar solvents are excellent in stability at high temperatures and are also preferred from the standpoint of availability.

[0059] When producing polyethernitrile, water is produced as a by-product as the reaction proceeds. In order to remove the by-product water, an organic compound that forms an azeotropic mixture with water can be added as needed. Such an organic compound is not particularly limited as long as it forms an azeotropic mixture with water, but a non-polar organic solvent having a boiling point lower than that of the reaction solvent is preferred, and specifically, toluene can be mentioned.

[0060] The method for producing the polyethernitrile of the present invention is usually carried out under heating in a nitrogen atmosphere or under reduced pressure. The reaction temperature can be varied over a wide range, but is preferably 80°C or higher, more preferably 150°C or higher. From the viewpoint of productivity, the reaction temperature is preferably 400°C or lower, more preferably 350°C or lower. Taking into account the sublimability and reactivity of the compound used, the reaction is preferably carried out at a temperature in the range of 150 to 350°C, more preferably 150 to 200°C, with the temperature being increased stepwise.

[0061] The polyethernitrile of the present invention can be obtained by separating and recovering it from the reaction mixture obtained as described above. The reaction mixture obtained by the above production method contains at least the polyethernitrile, and may contain other components such as oligomers, by-product salts, and unreacted base. There are no particular limitations on the method for recovering the polyethernitrile from such a reaction mixture, and examples include a method of recovering the polyethernitrile by contacting it with a solvent that can dissolve the by-product salts, if necessary, under heating, and a method of removing the by-product salts and oligomers under reduced pressure.

[0062] Generally, a solvent having a relatively high polarity is preferably used as a solvent capable of dissolving the by-product salt. The preferred solvent differs depending on the type of base and by-product salt used, and therefore cannot be limited. Examples of the solvent include water; alcohols such as methanol, ethanol, propanol, isopropanol, butanol, and hexanol; ketones such as acetone and methyl ethyl ketone; acetates such as ethyl acetate and butyl acetate; nitrogen-containing polar solvents such as N-methyl-2-pyrrolidone (NMP), N-methylcaprolactam, N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), 1,3-dimethyl-2-imidazolidinone (DMI), hexamethylphosphoramide, and tetramethylurea; sulfoxide / sulfone solvents such as dimethyl sulfoxide (DMSO), dimethyl sulfone, diphenyl sulfone, and sulfolane; and acids such as acetic acid, hydrochloric acid, sulfuric acid, and nitric acid. From the viewpoints of availability and economy, a solvent selected from water, methanol, acetone, acetic acid, hydrochloric acid, sulfuric acid, and NMP is preferred, and water, acetic acid, hydrochloric acid, and NMP are more preferred. These solvents may be used alone or in combination of two or more.

[0063] In the method of removing oligomers under reduced pressure, the reaction may be carried out under a pressure ranging from 0.001 to 1 atmosphere, if necessary, under heating, after the completion of the reaction.

[0064] The polyethernitrile particles of the present invention can be obtained by a method of precipitating polyethernitrile particles from a solution in which the polyethernitrile of the present invention is dissolved. This process is called particle formation. In this case, solid polyethernitrile may be dissolved in an organic solvent, and then the polyethernitrile may be particle formed from the solution. However, since the number of steps can be reduced, it is preferable to particle form the polyethernitrile directly from the reaction mixture in which the polyethernitrile is dissolved obtained as described above.

[0065] When producing the polyethernitrile particles of the present invention, the polyethernitrile particles can be precipitated by discharging a polyethernitrile solution into a mixture of a good solvent and a poor solvent, thereby obtaining the polyethernitrile particles.

[0066] The good solvent for polyethernitrile is not limited as long as it dissolves polyethernitrile, and may be a solvent in which polyethernitrile dissolves under heating. Specific examples of such solvents include nitrogen-containing polar solvents such as N-methyl-2-pyrrolidone (NMP), N-methylcaprolactam, N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), 1,3-dimethyl-2-imidazolidinone (DMI), hexamethylphosphoramide, and tetramethylurea; sulfoxide / sulfone solvents such as dimethyl sulfoxide (DMSO), dimethyl sulfone, diphenyl sulfone, and sulfolane; nitrile solvents such as benzonitrile, diaryl ethers such as diphenyl ether, ketones such as benzophenone and acetophenone; and mixtures thereof. When polyethernitrile is granulated from the reaction mixture, a solvent selected from NMP, DMSO, and sulfolane, which are particularly preferably used as reaction solvents, is preferred.

[0067] The poor solvent is not limited as long as it is miscible with the good solvent for polyethernitrile and does not dissolve polyethernitrile. Specific examples of the poor solvent include methanol and water.

[0068] For example, the polyethernitrile can be granulated by discharging the reaction solution after the reaction into a receiving vessel containing a mixed solvent of NMP:water = 8:2 (volume ratio). In this case, the number average particle size of the obtained polyethernitrile particles can be controlled by the type and composition of the poor solvent. For example, by reducing the proportion of water, particles with a smaller number average particle size can be obtained.

[0069] The particles or polymer lumps thus obtained can also be pulverized to form particles having a desired number average particle size.

[0070] The present invention will be described in more detail below with reference to examples, which are illustrative and not limiting.

[0071] <Proton NMR Measurement> Proton NMR measurement was performed using a JNM-ECZ-500R manufactured by JEOL Ltd., by dissolving the sample in a mixed solvent of pentafluorophenol / d2 chloroform = 5 / 4 (volume ratio). From the obtained spectrum, "integral value of peak A / integral value of peak B" and "integral value of the peak showing the terminal (integral value of peak (A + C)) / integral value of peak B" were calculated. Peak A: A peak having a peak top at 7.10 to 7.20 ppm Peak B: A peak having a peak top at 7.55 to 7.68 ppm Peak C: A peak having a peak top at 6.95 to 7.00 ppm.

[0072] <Melting Point> The melting point was measured by differential scanning calorimetry (DSC). The DSC measurement was performed using a Q20 manufactured by TA Instruments. The sample was heated from 50°C to 400°C at a heating rate of 20°C / min, held at 400°C for 1 minute, then cooled from 400°C to 50°C at a heating rate of 20°C / min, heated again from 50°C to 400°C at a heating rate of 20°C / min, held at 400°C for 1 minute, and then cooled from 400°C to 100°C at a heating rate of 20°C / min. The melting point was the value obtained during the second heating.

[0073] <Thermogravimetric analysis (TG)> The weight loss rate when held at melting point + 30°C for 30 minutes was measured using a TGA7 manufactured by PerkinElmer. After holding at 50°C for 1 minute under air flow, the sample was heated to melting point + 30°C and held at melting point + 30°C for 30 minutes to determine the weight loss rate. When calculating the weight loss rate, the weight after holding at 50°C for 1 minute was used as the reference weight.

[0074] <Melt Viscosity> The viscosity increase rate was measured using a rheometer. The rheometer was a Physica MCR501 manufactured by Anton Paar, and measurements were performed at an oscillation angle of 1000 Pa and an angular frequency of 6.28 rad / s. The sample was kept at the melting point + 30°C in air for 30 minutes, and the viscosity increase rate was calculated from the change in melt viscosity before and after heating.

[0075] <Number average particle diameter of polyethernitrile particles> The number average particle diameter of polyethernitrile particles was calculated by observing the shape under a microscope. The microscope was a VHX-S650 manufactured by Keyence Corporation, and the diameters of 100 randomly selected particles were measured from micrographs taken at 100x magnification, and the average was calculated. When the particle shape was not a perfect sphere, the longest and shortest diameters were measured, and the average was used as the particle diameter.

[0076] <Raw materials used in the examples> Hydroquinone (Fujifilm Wako Pure Chemical Industries, Ltd.) Resorcinol (Fujifilm Wako Pure Chemical Industries, Ltd.) 4,4'-dihydroxybiphenyl (Tokyo Chemical Industry Co., Ltd.) 2,6-dichlorobenzonitrile (Tokyo Chemical Industry Co., Ltd.) Sodium carbonate (Kanto Chemical Co., Inc.) NMP (Fujifilm Wako Pure Chemical Industries, Ltd.).

[0077] Example 1: A 300 mL separable flask equipped with a stirrer, nitrogen inlet tube, and Dean-Stark tube was charged with 8.81 g (80.0 mmol) of hydroquinone, 13.93 g (81.0 mmol) of 2,6-dichlorobenzonitrile, and 10.18 g (96.0 mmol) of sodium carbonate. Under a nitrogen atmosphere, 80 mL of NMP and 3 mL of toluene were added, and the mixture was reacted at 160°C for 0.5 hours, followed by 8 hours at 200°C. After completion of the reaction, the reaction solution was discharged into a receiving vessel containing 300 mL of a mixed solvent of NMP:water = 8:2 (volume ratio), thereby forming polyethernitrile particles. The resulting polyethernitrile particles were washed three times with 300 mL of a mixed solvent of NMP:water = 8:2 (volume ratio) (room temperature), and then three times with 300 mL of warm water (80°C), followed by vacuum drying overnight at 80°C, yielding 13.6 g of white polyethernitrile particles.

[0078] As a result of proton NMR measurement, a peak (Peak A) derived from a hydroxyl group terminal was observed at 7.11-7.13 ppm, a peak (Peak B) derived from the benzonitrile skeleton of the main chain was observed at 7.59-7.62 pm, and a peak (Peak C) derived from a chloro group terminal was observed at 6.97-6.99 ppm. From the respective integrals, "integral value of Peak A / integral value of Peak B" and "integral value of Peak (A + C) / integral value of Peak B" were calculated. The obtained polyether nitrile was analyzed, and the "integral value of Peak A / integral value of Peak B", "integral value of Peak (A + C) / integral value of Peak B", melting point, weight loss rate in air, viscosity increase rate in air, and number average particle size were as shown in Table 1.

[0079] Examples 2 to 9, Comparative Examples 1 to 6 The same operations as in Example 1 were carried out, except that the type and amount of the aromatic compound substituted with two hydroxyl groups, the amount of 2,6-dichlorobenzonitrile, the amount of sodium carbonate, and the polymerization time (holding time after reaching 200°C) were changed as shown in Tables 1 and 2. The obtained polyethernitrile particles were analyzed, and the "integral value of Peak A / integral value of Peak B," "integral value of Peak (A+C) / integral value of Peak B," melting point, weight loss rate in air, viscosity increase rate in air, and number average particle size are shown in Tables 1 and 2.

[0080]

[0081]

[0082] [Example 10] The particles obtained in Example 1 were pulverized in a counter jet mill to obtain polyethernitrile particles having a number average particle size of 1.2 µm. The obtained polyethernitrile particles were analyzed, and the "integral value of Peak A / integral value of Peak B," "integral value of Peak (A+C) / integral value of Peak B," melting point, weight loss rate in air, and viscosity increase rate in air were equivalent to those of the polyethernitrile particles obtained in Example 1.

[0083] Example 11 The same procedure as in Example 1 was carried out, except that the post-polymerization post-treatment method was changed to discharging the reaction solution into a receiving vessel containing 300 mL of a mixed solvent of NMP:water = 6:4 (volume ratio) to form polyethernitrile particles. The resulting polyethernitrile particles were washed three times with 300 mL of a mixed solvent of NMP:water = 8:2 (volume ratio) (room temperature) and then three times with 300 mL of warm water (80°C), and then vacuum dried overnight at 80°C. The resulting polyethernitrile particles were analyzed, and the "integral value of peak A / integral value of peak B," "integral value of peak (A + C) / integral value of peak B," melting point, weight loss rate in air, and viscosity increase rate in air were equivalent to those of the polyethernitrile particles obtained in Example 1. The number average particle size of the polyethernitrile particles was 180 μm.

[0084] The results of Examples 1 to 9 show that when the "integral value of Peak A / integral value of Peak B" is in the range of 0.050 or less, the thermal stability (weight loss rate in air, viscosity increase rate in air) is superior to that of Comparative Examples 1 to 6, in which the "integral value of Peak A / integral value of Peak B" is in the range of more than 0.050.

[0085] On the other hand, when the type and amount of the aromatic compound substituted with two hydroxyl groups and the amount of 2,6-dichlorobenzonitrile are the same as in Comparative Examples 1 to 5, the "integral value of Peak A / integral value of Peak B" tends to be greater than 0.050.

[0086] Note that Comparative Example 6 corresponds to Example 1 of International Publication No. WO2021 / 21492, and has an "integral value of peak A / integral value of peak B" greater than 0.050. Compared with Comparative Example 6, Examples 7 and 8 of the present application have a smaller "integral value of peak A / integral value of peak B", and are superior in thermal stability (weight loss rate in air, viscosity increase rate in air).

Claims

1. A polyethernitrile represented by formula (I), in which the "integral value of peak A / integral value of peak B" in proton NMR measurement measured using a mixed solvent of pentafluorophenol and deuterated chloroform in a volume ratio of 5:4 is 0.050 or less: Peak A: a peak having a peak top at 7.10 to 7.20 ppm Peak B: a peak having a peak top at 7.55 to 7.68 ppm In formula (I), Ar is a unit represented by any one of formulas (a) to (f), and Ar may be composed of one type or two or more types of units.

2. The polyether nitrile according to claim 1, in which the "integral value of the peak showing the terminal / integral value of peak B" is 0.001 to 0.055 in proton NMR measurement using a mixed solvent of pentafluorophenol and deuterated chloroform in a volume ratio of 5:

4.

3. The polyethernitrile according to claim 1 or 2, wherein Ar is composed of two or more types of units.

4. Polyethernitrile particles made of the polyethernitrile according to claim 1 or 2, having a number average particle size of 0.1 to 200 μm.

5. A mobility component comprising the polyethernitrile according to claim 1 or 2.

6. A structural material member comprising the polyethernitrile according to claim 1 or 2.

7. An electric / electronic material comprising the polyethernitrile according to claim 1 or 2.

8. Mobility using the mobility component according to claim 5.

9. A structural material using the structural material member according to claim 6.

10. An electric or electronic product using the electric or electronic material member according to claim 7.

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